Sulphonation of oils and greases



Patented May 5, 1936 Y UNITED STATES PATENT OFFICE SULPHONATION F OILS AND GREASES Alexander Gressner, Habana, Cuba No Drawing. Application May 29, 1934, Serial No. 723,183

Claims. (CI. 87-12) This invention relates to the sulphonation of bly augments the quantity of organically combined oils and greases (either aliphatic or aromatic oils, Y sulphuric acid as compared with previous procsaturated or non-saturated oils and greases, as esses, in which as much as 35% of the sulphuric well as their ethers and esters, especially of the acid employed does not enter into the reaction.

5 glycerylic group of drying, semi-drying or perma- The sulphuric acid is either poured all at once, or 5 nent oils or fats with high or medium iodine inaproperly graduated stream, into the substance number, as, e. g., the oils and fats of fiuvial-, to be sulphonated, according to the cooling calacustrine-, or marine-animal origin, with or withpacity of the vat, in order to avoid a sudden and out the presence of non-saponifiable substances) excessive rise of temperature which would result for use as lubricators, softeners, sizings, mordants, in diminishing the commercial value of the prod- 10 color enhancers, etc. in the textile, tanning and uct. After all the acid has been poured into the dyeing industries as, e. g. fibre spinneries, weavsulphonating cooling vat, stirring is continued eries, leather tanning and conditioning plants, etc. from thirty to sixty minutes longer, during which My process allows the sulphonation of organic time the reaction will be thoroughly completed. products (mentioned above) for the purpose of Immediately afterwards is added any hydrocar- 5 converting said organic substances into emulsive, bon or hydrocarbons which itis desired to embody dispersive, and miscible compounds of high stain the compound for the purpose of forming an bility, which may be readily incorporated with emulsion, dispersion or solution; while this mixfiuids and solvents as generally applied in the corture is being cooled down and briskly stirred, the

responding trades, as, e. g., water, alcohol of variexcess sulphuric acid is eliminated to the desired 20 ous strengths, etc. 7 1 point, preferably to the point where the pH value According to my process, said organic products is between 7 and 9, as I have discovered that neu- (more especially the fatty acids, their ethers and tralization to this value gives to my product its esters, and chiefly the drying semi-drying and improved emulsive, solutive and dispersive proppermanent oils or fats of animals having a fluvial, crties. It will be noted that the excess sulphuric 25 lacustrine, marine, or land habitat, also those of acid is neutralized after the addition of the ydr vegetable origin, with high or medium molecular carbon-and not before. This is a feature of my weight), acquire emulsive, dispersive, miscive and invention, h Presence of the Sulphuric acid solutive properties with which may be prepared allowing the sulphonated oil and the hydrocarbon solutions, suspensions, dispersions or emulsions to combine into a homogeneous and transparent with or without hydrocarbons or organic products mixture. Any one of the currently used alkalies having an acid, neutral, or basic reaction, as of will do,--as, e. g., hydroxides of soda or potash, mineral vegetable or animal oils and fats. The carbonates, 'bicarbonates, 28.89 liquid hydrocarbons'which I may use and incorporate monia, am The product ay w v r e into any oil or grease sulphonated accordingto made acid, neutral or basic, according to the'pur- 3.) my process are: all aliphatic saturated hydroc'arpose for which it is to be used. The resulting subbons (homologues of methane, hexane, heptane, stance is a clear viscous fluid. Mixed with water etc.) .also all aliphatic non-saturated. hydrocaror with other solvent, it will go into solution and bons (homologues of ethylene, propylene, etc.) yield snow-white emulsions of very high stability 40 also all aromatic hydrocarbons, as f. i. benzene which willkeep unaltered during many weeks. I 40 and its homologues, naphthalene, anthracene, yp a examples of Sulphonation according etc.; also all naphthenes or cycloparaflines (homoto my process are given below. I logues of trimethylene, heptamethylene, hexal. Incorporate, under the effects of a powerful naphthene, etc.) r and rapidly moving mechanical agitator or mixer,

My process consists in sulphonating one or sevvfi p r f completely dried and fi y p v r- 45 eral of the aforementioned oils or fats, either alone ized'acid sulphate of potash into one hundred or in the presence of mineral oils or greases, with parts'of sardine oil, or any similar oil, cooled with from ten to fifty percent, or greater percentage, ice or any other suitable means to +10 C. Alter of sulphuric acid, with or without the aid of tum-n thorough inc p of this caitflilyzer, p O- 5 ing sulphuric acid. The sulphonation is pernatlon is brought about by adding twenty parts formed in the presence of one or more acid sulof concentrated sulphuric acid, one half of which, phates of the alkaline metal group, as, for exi. e., ten parts, can be poured at. once into the ample, acid potassium sulphate (KHSO4). The vat. Due to the cooling and agitation, the ten 1 catalytic action of the group mentioned greatly perature willnot rise above 30 C. if no more than accelerates the sulphonic reaction and considerasaid ten parts of sulphuric acid were added at 55 once. Under continued stirring, and it the cooling is properly conducted, the temperature of the mixture will have descended again to the initial 10 C. within 20 minutes from the moment the first ten parts oi. sulphuric acid were added. At this time, the remaining ten parts of sulphuric acid can be added, either at once, or in a thick stream. The cooling and agitation are to be continued for an hour from the time the sulphonating process was started. One hour is enough to complete the sulphonic reaction, as it will be found that no more sulphuric acid will combine which mixture has the properties described and is homogeneous and transparent. Agitation during ten more minutes will bring about the de- 'sired homogeneity of the compound, after which the excess sulphuric acid is substantially removed by means. e. g., of sodium hydroxide in the form of lye of about 16 B. until the pH value is between 7 and 9. The lye is added in a thin stream (whilst stirring and cooling continue uninterrupted) until the compound turns to a yellowbrown color. At this moment, a small quantity placed in a test tube will show it to be clear. Upon .mixing the resulting product with water it will go at once into solution and form an emulsion oi! high stability in which dispersion or subdivision reaches the point where the Brownian movement can be detected.

2. Incorporate, under the effects of a powerful and rapidly moving mechanical agitator or mixer, five parts of benzol and five parts of naphthalene (both oi ordinary commercial grade and purity),

within an oil mixture obtained with ten parts of castor oil (oleum ricini), ten park-o1 liquid fatty acids of common tallow (oleic acid, red 011),.

twenty parts of herring oil with an iodine number ranging between 160 and 180, and fifty parts of ordinary sardine oil. Once the benzol and the naphthalene are completely dissolved in this mixture, incorporate five to eight parts of completely dried and finely pulverized acid sulphate of potash. The mixture should be cooled down to C. After thorough incorporation of this catalyzer, sulphonation is brought about by add-' ing thirty parts 01 concentrated sulphuric acid.

As in the previous formula, one halt of the quantity of this sulphuric acid, i. e., fifteen parts, can be poured at once into the vat. The temperature should not rise above 30 C. and, after about 20 minutes, should be down again to the 1mm! +5" C. if stirring and cooling were properly conducted.

The remaining fifteen parts oi? sulphuric acid are then added, not all at once, but in the form of a thin stream so that the temperature will not rise abov' e 30 C. After one full hour from the time the operation was started, the sulphonic reaction is completed. Similarly as with the first formula, from two hundred sixty to three hundred parts oi refined mineral oil with a specific weight of about .800, are now added all at once. Agitation during ten more minutes will bring about the desired homogeneity, after which neutralization is performed as in the first formula. Upon mixing with water the resulting product, it will go at once into solution and form an emulsion of high stability, in which dispersion or subdivision reaches the point where the Brownian movement can be detected. This product has eminent solutive, emulsive, dispersive, penetrating, lubricat- -ing, softening, and color enhancing properties,

and carries with it into emulsion or dispersion any other oils or greases added thereto. The

properties with which-it is endowed make it especially useful in the textile, tanning and dyeing industries.

What is claimed as new is:

1. In the sulphonation ofoils and greases con-,

taining oleaginous material, the step'comprising sulphonating the oleaginous material in the presence of an acid sulphate of an alkali mrtal at a rate to limit the temperature rise to approximately 30 C.

2. In the sulphonation of oils and greases containing oleaginous material, the step comprising sulphonating the oleaginous material with sulphuric acid in the presence of acid potassium sulphate at a rate to limit the temperature rise to approximately 30'C.

3. In the sulphonation of oils and greases containing oleaginous material, the steps comprising sulphonatlng the oleaginous material with an excess of sulphuric acid in the presence of an acid sulphate of an alkali metal at a rate to limit the temperature rise to approximately 30 0., adding and mixing a hydrocarbon and then substantially eliminating the excess sulphuric acid.

4; In the sulphonation of oils and greases containing oleaginous material, the steps comprising sulphonating the oleaginous material with acid sulphate of an alkali metal at a rate to limit the temperature rise to approximately 30 C., adding and mixing a hydrocarbon and then add- 7 an excess of sulphuric acid in the presence of an ing an alkali until the pHvalue is from 7 to 9.

5. In the sulphonation of oils and greases containing oleaginous material, the steps comprising sulphonating the oleaginous material with an excess of sulphuric acid in the presence of an acid sulphate of an alkali metal at a rate to limit the temperature rise to approximately 30 C.,

adding and mixing a hydrocarbon and then substantially eliminating the excess sulphuric acid by neutralization.

ALEXANDER GRESSNER. 

